Alkoxy esters of polybasic organic acids



Patented Mar. 26, 1929.

UNITED STATES- P-A'U'ENT; OFFICE.

30m n 1:. van scnucx, m, or Evms'ron, m sonar lcnvnnr, or wrmm'r'm,

ILLINOIS, ASSIGNOBS TO VAN SOHAACK BROS. CHEMICAL "WORKS, 1170., 01' CHI OLGO, ILLINOIS, A CORPORATION OI ILLINOIS.

.uxon mm or ronnasrc onenuc ACIDS.

ll'o Drawing.

, This invention relates to a composition of matter comprising an alkoxy ester of a polybasic organic acid.

An example of the invention isdiethmty- 5 ethyl phthalate,

be varied.

If the digestion is conducted under a fractionating column, the top of which is allowed to rise to or just slightly above the boiling point of water,the water formed may be continuously removed and the reaction thus permitted to proceed until nearly all of the phthalic anhydride is esterified.

After a large part. of the phthalic anhy- I dride is esterified, the mixture is made su stantially neutral by agitation with an aqueous solution of 10 pounds of sodium carbonatein 100 pounds of water, washed, by agitation with water, and then submitted to vaclium distillation. A fraction containing 86 such impurities as water, uncombined glycolmonoethyl ether, and free phthalic anhydride is first obtained. Then there is o tained a fraction boiling at 205 C. at a pressure equal approximately to 4 mm. of mercury. This fraction contains diethoxyethyl phthalate. To purify the fraction, it may be neutralized as before, washed with water, and redistilled in vacuo,the foreshot being again discarded. The fraction boiling at 200-2 C. agapproximately 4 mm. is diethoxy ethyl phtha a In another preparation there was used 146' parts by weight of phthalic anhydride, 216 parts ethoxyethano (glycol monoethyl ether), 10 arts sulfuric acid, and 200 parts benzene. he mixture was heated to boiling ---and kept boiling for 5 hours. The vapors formed were passed up through a tube and Application October 81, 1827. Serial Io. 230,181.

then down through a water-cooled condenser.

"The condensate was collected in a receiver from which the lower, aqueous layer was withdrawn from the bottom and the upper layerreturned to still. After 5 hours it was found that 22.4 parts of lower layer had been collected and that only 4.2% of the total, original acidity remained. In other words, 95.8% of the phthalic anhydride had been esterified. The reaction mixture was then neutralized with an excess of sodium carbonate above that required forthe free acidity.

The neutralized product was then distilled" in vacuo. The main .fraction, boiling at 200-2l1 C.- at approximately 4 mm. of mercury pressure, amounted to 186 parts and consisted of diethoxy ethyl phthalate of such purity as to constitute a desirable plasticizer for la uer.

Details of the method of preparation may Also, we may use some other alkoxy alcohol than ethoxyethanol. Thus we may. use, for example, butoxyethanol (HO.QH,.CH,.OG H,) ethoxypropanol v (HO.CH .CH,.GH .OC,H,) or ethoxy-secondary-butanol v CH,.CHOH.GH,.CH .OC H

We may use the alkoxy alcohol in amount equivalent to or in excess of the phthalic anhydride, to esterify both of the acidic groups of phthalic acid (or phthalic anhydride).

Or, we may use only enou h of the alkoxy alcohol to form alkoxyalkyl ydrogen phthalor an aliphatic alcohol, as, for example ethyl,

isopropyl, butyl, or amyl alcohol.

To prepare butyl ethoxyethyl phthallate,

for example, we may-proceed as follows:

Monobutyl phthalate was first prepared from 148 g. of phthalic anhydride and 7 5 g.-

of butyl alcohol by warming them together for a few minutes in the presence of 50 cc. ofbenzene and of H SO Then g. of ethoxy ethyl alcohol was added and the mixture was heated 8 hours at a temperature I than phthalic or a polybasic acid. Thus I distilled ofi' at 40. mm. pressure. The re-' mainder was distilledunder greatly reduced pressure. The principal fraction distilled at 182-185 C. at approximately 5 mm. pres sure.

The butyl ethoxyethyl phthalate was a clear colorless liquid of which 1 cc. weighed 1.08 g. at 20 C.

Also, I may use some other dibasic acid may use citric, tartaric, succinic, phenyl malonic acid, or trimesic acid, C H (COOH) Some specific examples and type formulas of the compounds within the scope of my inin which R represents any 35 vention follow:

1. e ngooocn on oozHaz Diethoxyethyl phthalate 2. nuoooen on oo ng in which R represents any divalent group of atoms comprising carbon and hydrogen.

a. nucoocn en oe nm,

polyvalent group of atoms comprising car on and hydrogen and 0: represents an integral number which is not less than 3.

4. (].,H (COUCH (CH .OH .CH .OC H 2 Dl-ethoxy-secondarybutyl phthalate.

I Ethoxyethyl butyl phthalate 000011 011 003, 6. c,H,

coocn cn o n R eoon in which R and R represent respectively the radicals as above stated.

I COORDR s. R

- COO .R

in which R and R represent respectively the nuance radicals as above stated, R (represents any divalent and R any monovalent' group of carbon and hydrogen atoms. Thus B. may be an alkylene radical, as, for example,

CH CH GH CH CH -CH(Cl-I .GH .CH or CH' .CH(CH .CI-I,,.CH and B may be an alkyl radical, as for example, CH 62H. 03111: 04H": s na 9. Compounds of the type described in Example No. 8 but in which R represents specifically the group GH .CH as, for example, in the following:

A citrate in which R represents an alkoxyalkyl, alkoxyaryl, or aryloxyaryl radical and R and R represent either additional radicals of the same type or alykyl or aryl radicals, no one radical containing more than eight carbon atoms.

The various compounds may be made from the esterification of the acid, Whose radical appears in the final product, with the alkoxy alcohol, aryloxy alcohols, or other alcohol whose radicals are also in the final product. The technique of such esterifications and means of purification have been illustrated by specific examples.

When the radicals R to'R inclusive contain each not more than four carbon atoms, in addition to those carbons occurring in a benzene ring, the esters described, in liquid form, are excellent solvents for pyroxylin, with which they may be used as a plasticizer. The great majority of these esters are liquids at ordinary temperatures or melt at a lower temperature than camphor, which they may substitute to advantage.

The following illustrations show compositions comprising pyroxylin and a typical one of new esters. All ,proportionsare by weight. A Lacquer fiI/m. Formula #1.

Parts.

which the hydrogen of at least oneof the carthe acid is re lacedb an boxyl u s ""f alkoxy l yiza lical .and the hy rogen 0 another carboxyl group is replaced by an alkyl Pyroxylin 3 g o p- Eth th l b t l phthalate 1 7 An ester of a dicarboxyhc acid In which P la I p v the hydrogen of at least one of the. carboxyl W m mula parts groups of the acid is replaced by an alkoxypyroxylin al radical and the hydrogen of the other Ethoxyethyl butyl phthalate 1 car y group 18 replaced b 1 alkyl g p- Bu'tyl acetate"; 15 8. an ester of a dicarboxy 1c aromatic acid Butanol 5 m whlch the hydrogen of at least one of the Ethyl acetate; 5 carboxyl groupsof the acid is replaced b an a 1 5 alkoxyalkyl radical and the hydrogen 0 the 1 I 20 other carboxyl group is replaced by an alkyl 0 h 10 group- 58 f 9. An ester of a phthalic acid in which the P q Formukl' hydrogen of .at least one of the carboxyl Parts. groups of the acid is replaced by an alkoxy- F rm l 64 a] l radical and the hydrogen of the other Ester gu 2 car ox l-group-is rfeplacpld by an alkyl group. 1 n ester 0 ort ohtha ic acid in Pzgmme'd lat/gun R parts. which the hydrogen of at least one ofthe Formula #3 66 carboxyl groups of the acid is, replaced b an 'Zinc oxide 1 alkoxyalkyl radical and the hydrogen 0 the By alkoxyalkyl as used in the specifications and claims we mean a monovalent group of atoms containing hydrogen, carbon,

and oxygen, the one oxygen atom being linked, as an ether oxygen, between two carbon atoms, as in the ethoxyethyl radical,

We claim: H

1. An ester of a polycarboxylic acid in which the hydrogen ofat least one of the carboxyl groups of the acid is replaced by an alkoxyalkyl radical that contains at least four carbon atoms.

2. An ester of a dicarboxylic acid in which the hydrogen of at least one of the carboxyl groupsof the acid is replaced by an alkoxyalkylradical that contains at least four carbon atoms.

3. An ester of a dicarboxylic aromatic acid inwhich the hydrogen of at least one of the carboxyl groups of the acid is replaced by an alkoxyalkyl radical that contains at least four carbon atoms.

4. An ester of a phthalic acid in which the hydrogen of at least one of the carboxyl groups of the acid is replaced by an alkoxyalkyl radical that conta ns at least four carbon atoms.

5. An ester of an orthohthalic acid in which the hydrogen of at east one of the carboxyl groups of the acid is replaced b an I alkoxyalkyl radical that contains at east .four carbon atoms.

6. An ester of a polycarboxylic acid in i in which R re resents any divalent group of carbon and ydrogen atoms and'It any monovalent group of carbon andhydrogen atoms.

12. A composition of matter comprising the grouping of atoms as shown in claim 11, R representing the group CH,.GH, and R any monovalent group of carbon and hydrogen atoms. 13. A composition of matter comprising the grouping of atoms shown in claim 11, R representing the group -CH .CH and R? the eth lradical, --C,H

14. composition of matter comprising the grouping of atoms represented by the formula n oo.m

in which R and R represent, respectively,

divalent and monovalent groups containing only carbon and hydrogen atoms and'R? represents any monovalent radical containing only carbon and hydrogen atoms.

15. A composition of matter comprising the grouping of atoms represented by the I following formula 5 H oonuom 11 oooomcmLomcni in which R and R represent divalent and monovalent groups, respectively, of carbon and hydrogen. I is:

v 16. 'A composition of matter comprising the grouping of atoms represented by the u formula H ooo.om,on,.o.o,m

17. A composition of matter comprising ethoxyethyl butyl ortho-phthalate, a colorless liquid boiling at 1825 C. at a pressure of approximately 5 mm. of mercury.

18. An ester of a polycarboxylic acid in which the hydrogen of at least one of the car-- boxyl groups is replaced by a monovalent group containing carbon and hydrogen atoms and only one oxygen atom, the oxygen atom being combined, in a so-called ether linkage, to carbon atoms of two radicals that con ain each at least two carbon atoms.

which the hydrogen of at least one of the carboxyl groups is replaced by a monovalent 45 group containing carbon and hydrogen atoms and only one oxygen atom, the oxygen atom being linked between two carbon atoms in a so-called ether linkage and the hydrogen of another carboxyl .group of the acid is re- 50 placed by an alkyl group.

ROBERT H. VAN SCHAACK, JR. ROBERT CALVERT. 

